Cosmetic preparations



2,794,765 Patented June 4, 1957 COSMETIC PREPARATIONS Otto Albrecht, Neuewelt, near Base], and Erich Matter, Riehen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application August 8, 1955, Serial No. 527,127

9 Claims. (Cl. 167-87) It is known that cation-active compounds can be used for making detergent preparations for the hair. Such compounds, as compared with anion-active detergents, generally have the advantage that they favorably influence the properties of the hair. The feel, softness and combability of the hair is substantially improved, and the hair acquires a beautiful gloss and impoverished and attacked hair is strengthened so that its further treatment is facilitated. In addition to'this advantage, the cation-active compounds hitherto used for this purpose, as compared with anion-active products, have the disadvantage that solutions thereof do not foam sufliciently.

The present invention provides cosmetic preparations, especially cation-active detergent preparations for the hair having good foaming properties, which contain a water-soluble quaternary ammonium salt which contains at least one non-aromatic hydrocarbon radical of more than 7 carbon atoms and, bound to the quaternary nitrogen atom, a radical of the formula in which R1 represents an alkylene radical which con tains at most 7 carbon atoms and may be interrupted by hetero-atoms, R2 and R3 each represent hydrogen or an alkyl or substituted alkyl radical.

In the ammonium salts used in this invention the nonaromatic hydrocarbon radical containing more than 7 carbon atoms may be bound directly to the quaternary nitrogen atom. Accordingly, when the hydrocarbon radical is an alkyl radical these compounds can be regarded as derivatives of alkylamines of high molecular weight, for example, of octylamine, octadecylamine, oleylamine and especially of dodecylamine. It is, however, of advantage to use compounds in which at least one hydrocarbon radical containing more than 7 carbon atoms is bound to the quaternary nitrogen atom through one or more hetero-atoms. As heteroatoms there come into consideration especially oxygen or nitrogen atoms, which may form part of functional groups or heterocyclic rings. As functional groups there may be mentioned ether groups and especially acyl groups, such as ester or amide groups. When an ester group is present the products used in the invention may be derived from non-aromatic carboxylic acid, for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and an alkanolamine containing at least one amino group such, for example, as dimethyl-ethanolamine, dipropyl-ethanolamine or triethanolamine. When an amide group is present, the compounds may be derivatives of the carboxylic acids mentioned above with a dior poly-amine such, for example, as ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine or tetraethylene peutamine, or from hydroxylalkylation products of such dior polyamines, such as dihydroxyethyl-ethylene diamine or trihydroxyethyl-ethylene diamine. When at least one nonaromatic hydrocarbon radical having more than 7 carbon atoms i bound to the quaternary nitrogen atom through a heterocyclic radical, the latter is advantageously imidazoline ring. Such imidazoline derivatives having a hydrocarbon radical of high molecular weight and a side chain containing nitrogen are described in U. S. patent application, Serial No. 467,639, filed November 8, 1954, by Otto Albrecht.

The aforesaid atomic grouping of the formula in which R1 represents an alkylene radical which contains at most 7 carbon atoms and may be interrupted by a heteroatom, and R2 and R3 represent hydrogen or an alkyl or substituted alkyl radical which is bound to the quaternary nitrogen atom in the compounds used in the invention, is the radical of an aliphatic carboxylic acid amide, for example, of caproic acid diethyl amide, acetic acid methyl amide and especially acetamide.

In the cosmetic preparations of the invention there are advantageously used compounds which contain only one hydrocarbon radical having more than 7 carbon atoms and in which this radical contains 10-18 carbon atoms, or, if more than one such hydrocarbon radical is prescut, the sum of the carbon atoms in such radicals does not exceed 20.

The compounds used in this invention are advantageously prepared by first preparing a compound containing at least one hydrocarbon radical having more than 7 carbon atoms and a tertiary nitrogen atom, and then reacting the resulting intermediate product with a compound capable of introducing the radical The aforesaid intermediate product is advantageously prepared by acylating an alkanolamine or dior polyamine mentioned above with a carboxylic acid of the kind mentioned above or a functional derivative thereof, such as an acid chloride, ester or anhydride thereof, and, if no tertiary amino group is present in the starting materials, introducing a tertiary amino group by alkylation or hydroxyalkylation, and especially by hydroxyethylation by means of ethylene oxide. When the intermediate product is to be an imidazoline derivative, it can be prepared in the manner described in U. S. patent application, Serial No. 467,639, filed November 8, 1954, by Otto Albrecht. As compounds introducing the radical of the above formula there are advantageously used the corresponding halogen-carboxylic acid amides, especially chloracetamide. The compounds can also be synthesized in another manner, for example, by first preparing a compound which contains the quaternary nitrogen atom to which the acid amide grouping is bound, and subsequently introducing the hydrocarbon radical having more than 7 carbon atoms. The various reactions may be carried out by methods in themselves known.

Since it is of advantage to use halogen-carboxylic acid amides for making the compounds used in the invention, the quaternary ammonium salts will usually contain as the anion a halogen-ion, and especially a chlorine-ion. These halogen-ions may of course be exchanged for the anions of other inorganic or organic acids.

It is of advantage to impart to the cosmetic preparations of the invention an acid reaction. The pH value may be suitably adjusted by the addition of a compound of acid reaction. As such compounds there may be used salts of acid reaction. such as primary phosphates, or more especially organic acids of the kind customarily used for this purpose in cosmetic preparations, for example, aliphatic hydroxy-carboxylic acids, such as glycollic acid or citric acid, and especially lactic acid.

In order to avoid or reduce any irritant action which may be caused by cation-active compounds in persons having very sensitive skin, there may be incorporated in the preparations of this invention water-soluble non-ionic compounds derived from mercapto-compounds containing a non-aromatic radical of at least 10 carbon atoms. These non-ionic water-soluble aliphatic mcrcaptan derivatives may be derived, for example, from dodecyl-mcrcaptan hexadecyl-mercaptan or octadecylmercaptan. There are advantageously used alkylene oxide condensation products, especially ethylene oxide condensation products. An especially suitable product is the compound obtainable from tertiary dodecyl-mercaptan and ethylene oxide, of which the turbidity point of a solution of 0.115 percent strength is about 69 C. and of which the refractive index for the D-line is 1.4685.

The detergent preparations for the hair or other cosmetic preparations of this invention, for example, those suitable for bleaching the hair, can be prepared by simple mixing and dissolution of the components. For this purpose there may be used, for example, a single member of: one class of compounds to be used, or a mixture of two or more compounds from the same class. There may also be incorporated additions such as are usual in detergent preparations for the hair, such as perfume, dycstull's, bleaching agents or thickening agents. It is especially advantageous to add fatty acid alkanolamides, for example, coconut oil fatty acid hydroxyethylamide. The new preparations may be made up in solid, paste-like or liquid form. They are used in known manner for treating the hair. The treated hair is generally well defatted, acquires a soft feel and a beautiful gloss and can be brushed easily, since its tendency to become electrically charged is considerably reduced.

Especially advantageous preparations are those which contain as the cation'active constituent a compound of the formula in which R1 represents an alkylene radical of low molecular weight, R2. Rs and R4 each represent a hydrogen atom or alltyl group of low molecular weight, R5 and Re each represent an alkyl group of low molecular weight, and R". represents an alkyl group of high molecular Weight containing. for example, 11-17 carbon atoms. These compounds. for example, those of the formula $1 Rs ll7-W-HN-R1-N curt;

in which R1. Rs. R0 and R7 have the meanings given above. yield not only advantageous hair washing preparations of good activity but possess an especially good resistance to oxidizing agents, such as hydrogen peroxide.

The following examples illustrate the invention, the

parts being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

Example 1 21.6 parts of the quaternary ammonium salt described below are mixed with 7 parts of lactic acid of. about percent strength, 7.85 parts of a water-soluble condensation product of tertiary dodecyl-mercaptan with ethylene oxide (for example, the product of which the turbidity point of a solution of 0.115 percent strength is about 69 C.), 4.9 parts of N-hydroxycthyl-coconut oil fatty acid amide, 2 parts of para-(stearoylamino)-phenyl-trimethylarnmonium methosulfate and 56 parts of water.

The quaternary ammonium salt mentioned above is prepared as follows:

28.3 parts of coconut oil fatty acid esterified with N:N- dimethyl-ethanolamine and 10.3 parts of chloracetamide are heated in a current of nitrogen in a boiling water bath, while stirring, until the reaction product is clearly soluble in water, which is the case in a short time.

Example 2 The procedure is the same as in Example 1, except that, instead of the quaternary ammonium salt obtained by reaction with chloracetamide, there is used the quaternary ammonium salt obtained as follows:

200 parts of distilled coconut oil fatty acid, 103 parts of diethylene triamine, 0.2 part of boric acid and 150 parts of xylene are heated under reflux until the elimination of water ceases. The xylene flowing from the reflux condenser, before it is returned to the reaction vessel, is passed through a water separator in which the water is continuously removed. After about 8 hours the reaction is finished, and the solvent is distilled off under reduced pressure. 148 parts of the imidazoline so obtained are heated at C. and then 44 parts of ethylene oxide are introduced in the form of a finely distributed gas stream at l20l25 C.

36.7 parts of the resulting hydroxyethylation product and 9.4 parts of chloracetamide are heated in a current of nitrogen in a boiling Water bath, while stirring, until the reaction product is clearly soluble in water, which is the case after a short time.

Example 3 The procedure is the same as described in Example 1, except that, instead of the quaternary ammonium salt obtained by reaction with chloracetamide, there is used the quaternary ammonium salt obtained as follows:

93 parts of the imidazoline mentioned in Example 2 and obtained from distilled coconut oil fatty acid and diethylene triamine, are heated at 120 C. and then 43 parts of propylene oxide are introduced in the form of a finely distributed gas stream at l20130 C.

18.7 parts of the resulting hydroxyethylation product and 4.7 parts of chloracetamide are heated in a current of nitrogen in a boiling water bath, While stirring, until the reaction product is clearly soluble in water, which is the case after a short time.

Example 4 The procedure is the same as in Example 1, except that instead of the quaternary ammonium salt described therein, there is used the quaternary ammonium salt obtained as follows:

5.6 parts of the acylation product of N:N-dimethylpropylene diamine with coconut oil fatty acid and 1.9 parts of chloracetamide are heated in a current of nitrogen in a water bath, during which the formation of the quarternary ammonium salt takes place in a short time. The quaternary ammonium salt is clearly soluble in water.

Example 5 The procedure is the same as described in Example 1,

except that, instead of the quaternary ammonium salt described therein, there is used the product prepared as follows:

4 parts of the acylation product of NzN-diethylpropylene diamine with commercial stearic acid and 0.94 part of chloracetamide are heated in a current of nitrogen in a boiling water bath for 6 hours while stirring. The quaternary ammonium salt so obtained is soluble in water.

Example 6 72.0 parts of the quaternary ammonium compound prepared as described in the second paragraph of Example 4, 1.16 parts of acetoacctylaminobenzene, 0.25 part of 8-hydroxyquinoline sulfate, 55.4 part of hydrogen peroxide solution of 35% strength, 0.16 part of phosphoric acid, and 0.32 part of acetic acid are dissolved with enough water to bring the volume of the solution up to 1000 parts by volume.

The resulting solution is a very well-foaming cationactive agent for the oxidative fixation of permanent waves produced by the cold or luke-warm method.

It is distinguished by a very favorable effect of the cation-active compound on the hair and also by the high degree of the effect produced by the foam. Moreover, the solution, when appropriately stored, does not lose any of its original hydrogen peroxide content.

Example 7 For washing living hair a solution of 20 parts of the product described in the first paragraph of Example 1 in 80 parts of warm Water is prepared. This solution is of acid reaction and foams strongly. Hair washed with the solution is well defatted and acquires, in addition to a beautiful gloss, a pleasant soft feel. Furthermore, the tendency of the hair to become electrostatically charged when brushed is considerably reduced.

What is claimed is:

1. A cation-active cosmetic preparation, which contains a major proportion of a water soluble quaternary ammonium salt which corresponds to the formula NHz in which R1 represents an alkylene radical containing at the most 3 carbon atoms, R5 and Rs each represent an alkyl radical containing at the most 2 carbon atoms and R7 represents an alkyl radical containing at least and at the most 18 carbon atoms and a minor proportion of a compound of acidic reaction.

2. A cation-active cosmetic preparation, which contains a major proportion of a water soluble quaternary ammonium salt which corresponds to the formula in which R1 represents an alkylene radical containing at the most 3 carbon atoms, R5 and Re each represent an alkyl radical containing at the most 2 carbon atoms and R7 represents an alkyl radical containing at least 10 and at the most 18 carbon atoms and a minor proportion of a compound of acidic reaction.

3. A cation-active cosmetic preparation, which contains a major proportion of a water soluble quaternary ammonium salt which corresponds to the formula in which R5 and Rs each represent a hydroxyalkyl group containing at the most 2 carbon atoms and R1 represents an alkyl radical containing at least 10 and at the most 18 carbon atoms and a minor proportion of a compound of acidic reaction.

4. A cation-active cosmetic preparation, which contains a major proportion of the quaternary ammonium salt of the formula and a minor proportion of a compound of acidic reaction.

5. A cation-active cosmetic preparation, which contains a major proportion of the quaternary ammonium salt of the formula and a minor proportion of a compound of acidic reaction.

7. A cation-active cosmetic preparation, which contains a major proportion of the quaternary ammonium salt of the formula and a minor proportion of a compound of acidic reaction.

8. A cation-active cosmetic preparation, which contains a major proportion of the quaternary ammonium salt of the formula and a minor proportion of a compound of acidic reaction. 9. A cation-active cosmetic preparation which contains in which R1 represents an alkylene radical containing at 10 the most 3 carbon atoms, R2 represents a member selected from the group consisting of lower alkyl and lower hydroxyalkyl radicals, R7 represents an alkyl radical containing at least 10 and at the most 18 carbon atoms, Y represents a member selected from the group consisting of O- and NH-, and n denotes a whole number or at the most 2; and a minor proportion of a compound of acidic reaction.

No references cited. 

1. A CATION-ACTIVE COSMETIC PREPARATION, WHICH CONTAINS A MAJOR PROPORTION OF A WATER SOLUBLE QUATERNARY AMMOMIUM SALT WHICH CORRESPONDS TO THE FORMULA 